Process for Preparing Imino Compounds

ABSTRACT

Process for preparing imine compounds, in which a carbonyl compound is reacted with a primary amine. The imine compound obtained in this way can be reacted further with a metalalkyl and subsequently a carbonyl compound to form an imine compound.

The present invention relates to a process for preparing imino compounds.

The use of metallocene catalysts in the polymerization of unsaturated compounds has a great influence on the preparation of polyolefins since it opens up a route to new types of polyolefinic materials or to materials having improved properties. There is therefore great interest in the development of novel families of catalysts for the polymerization of unsaturated compounds in order to obtain even better control over the properties of polyolefins and further novel products.

The use of transition metal catalysts comprising late transition metals is of particular interest due to their ability to tolerate heteroatom functions. Transition metal catalysts derived from late transition metals which are suitable for the polymerization of unsaturated compounds are known from the prior art. Among these, 1,2-diiminenickel and 2,6-bis(imino)pyridyliron complexes have been found to be particularly useful.

The preparation of unsymmetrical 2,6-bis(imino)pyridyl compounds which bear two different imino groups is usually carried out via a first condensation of the corresponding diketo compounds with a primary amine. The intermediate obtained is then reacted with a second primary amine which is different from the first. In the first step, not only the monoimine but also the symmetrical diimine product are formed, so that the yield of the intermediate is usually very low. Particularly when primary amines having electron-pulling or relatively nonbulky groups are used, the yield of monoimine intermediate drops.

WO 98/27124 discloses the synthesis of unsymmetrical 2,6-bis(imino)pyridyl compounds from the corresponding diketo compounds and anilines in toluene with addition of catalytic amounts of toluenesulfonic acid via monoimine intermediates. Monoimine intermediates having electron-pulling substituents are not disclosed.

When anilines which bear an electron-pulling substituent in the ortho position are used, the yield of monoimine intermediate is very low. It is an object of the present invention to provide an improved process for the synthesis of the monoimine intermediate, by means of which even primary amines having electron-pulling or relatively nonbulky substituents can be converted into the corresponding monoimine compounds in improved yields. These monoimine compounds are particularly well-suited as starting materials for the synthesis of unsymmetrical diimine compounds and lead to higher yields of unsymmetrical product.

We have accordingly found a process for preparing imine compounds of the formula I,

where the variables have the following meanings:

-   A¹ is chlorine, bromine or iodine, -   the radicals R¹ are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical or a five-, six- or seven-membered heterocycle     comprising at least one atom from the group consisting of N, P, O     and S, where the organic radical R¹ may also be substituted by     halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or the radical R¹ may also be     joined to R³ to form a five-, six- or seven-membered ring, -   R³-R⁵ are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical, NR¹¹ ₂, OR¹¹, halogen, SiR¹² ₃ or a five-, six- or     seven-membered heterocycle comprising at least one atom from the     group consisting of N, P, O and S, where the organic radicals R³-R⁵     may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or     two radicals R³-R⁵ may also be joined to one another to form a     five-, six- or seven-membered ring and/or two radicals R³-R⁵ may be     joined to one another to one another to form a five-, six- or     seven-membered heterocycle comprising at least one atom from the     group consisting of N, P, O and S, -   the radicals R¹¹ are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical or SiR¹² ₃, where the organic radicals R¹¹ may also be     substituted by halogens and two radicals R¹¹ may also be joined to     form a five- or six-membered ring and -   the radicals R¹² are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical and two radicals R¹² may also be joined to form a five-     or six-membered ring, -   G is C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₄₀-aryl, arylalkyl having     from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms     in the aryl radical, NR¹¹ ₂, SiR¹² ₃ or a five-, six- or     seven-membered heterocycle comprising at least one atom from the     group consisting of N, P, O and S, where the organic radical G may     also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃, -   E¹-E³ are each, independently of one another, carbon, nitrogen or     phosphorus, in particular carbon, and -   u is 0 when E¹-E¹³ is nitrogen or phosphorus and is 1 when E¹-E³ is     carbon,     which comprises the following steps:     A) reaction of a carbonyl compound of the formula II

with a primary amine G-NH₂, where the variables are as defined above.

Furthermore, we have found imine compounds of the formula I.

In the process of the invention, a primary amine is any compound which bears an NH₂ group, i.e. including hydrazines.

As primary amine, use is made of G-NH₂, where the meaning of G and its preferred embodiments is the same as for the imine compound of the formula I. Examples of primary amines are methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, sec-butylamine, isobutylamine, tert-amylamine, n-pentylamine, n-hexylamine, n-octylamine, cyclohexylamine, aniline, 2-methylaniline, 2-chloroaniline, 2-bromoaniline, 2,6-dichloroaniline, 2,4-dichloro-6-methylaniline and 2,6-dibromoaniline. G preferably comprises a halogen-comprising substituent.

Preference is given to imine compounds of the formula Ia,

where the variables have the following meanings:

-   A¹ is chlorine, bromine or iodine, -   the radicals R¹ are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical or a five-, six- or seven-membered heterocycle     comprising at least one atom from the group consisting of N, P, O     and S, where the organic radical R¹ may also be substituted by     halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or the radical R¹ may also be     joined to R³ to form a five-, six- or seven-membered ring, -   R³-R¹⁰ are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical, NR¹¹ ₂, OR¹¹, halogen, SiR¹² ₃ or a five-, six- or     seven-membered heterocycle comprising at least one atom from the     group consisting of N, P, O and S, where the organic radicals R³-R¹⁰     may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or     two radicals R³-R⁵ or two radicals R⁶-R¹⁰ may also be joined to one     another to form a five-, six- or seven-membered ring and/or two     radicals R³-R⁵ or two radicals R⁶-R¹⁰ may be joined to one another     to form a five-, six- or seven-membered heterocycle comprising at     least one atom from the group consisting of N, P, O and S, -   the radicals R¹¹ are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical or SiR¹² ₃, where the organic radicals R¹¹ may also be     substituted by halogens and two radicals R¹¹ may also be joined to     form a five- or six-membered ring and -   the radicals R¹² are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical and two radicals R¹² may also be joined to form a five-     or six-membered ring, -   E¹-E³ are each, independently of one another, carbon, nitrogen or     phosphorus, in particular carbon, and -   u is 0 when E¹-E³ is nitrogen or phosphorus and is 1 when E¹-E³ is     carbon.

Here, primary amines G-NH₂ used are anilines of the formula III

where the variables are as defined above.

G is preferably

where the variables have the following meanings:

-   R⁶-R¹⁰ are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical, NR¹¹ ₂, OR¹¹, halogen, SiR¹² ₃ or a five-, six- or     seven-membered heterocycle comprising at least one atom from the     group consisting of N, P, O and S, where the organic radicals R⁶-R¹⁰     may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or     two radicals R⁶-R¹⁰ may also be joined to one another to form a     five-, six- or seven-membered ring and/or two radicals R⁶-R¹⁰ are     joined to one another to form a five-, six- or seven-membered     heterocycle comprising at least one atom from the group consisting     of N, P, O and S, -   the radicals R¹¹ are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical or SiR¹² ₃, where the organic radicals R¹¹ may also be     substituted by halogens and two radicals R¹¹ may also be joined to     form a five- or six-membered ring and -   the radicals R¹² are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical and two radicals R¹² may also be joined to form a five-     or six-membered ring.

The three atoms E¹ to E³ of the imine compound of the formula I or Ia and of the carbonyl compound II can be identical or different. E¹ to E³ are each nitrogen, phosphorus or carbon, in particular nitrogen or carbon and particularly preferably carbon.

The substituents R¹ of the imine compound of the formula I or Ia and of the carbonyl compound of the formula II can be varied within a wide range. Possible carboorganic substituents R¹ are, for example, the following: C₁-C₂₂-alkyl which may be linear or branched, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5- to 7-membered cycloalkyl which may in turn bear a C₁-C₁₀-alkyl group and/or C₆-C₁₀-aryl group as substituent, e.g. cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C₂-C₂₂-alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C₆-C₂₂-aryl which may be substituted by further alkyl groups, e.g. phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5- or 2,6-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl, or arylalkyl which may be substituted by further alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, where, if appropriate, a radical R¹ may also be joined to R³ to form a five-, six- or seven-membered ring which may also be a heterocycle comprising at least one atom from the group consisting of N, P, O and S. The organic radicals R¹ may also be substituted by halogens such as fluorine, chlorine or bromine, by amino NR¹¹ ₂, for example dimethylamino, n-pyrrolidinyl or picolinyl, by alkoxy or aryloxy OR¹¹, e.g. methoxy, ethoxy or isopropoxy, or organosilicon substituents SiR¹² ₃, e.g. trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, tri-tert-butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. Possible substituents R¹¹ are the same carboorganic radicals as described above for R¹, where, if appropriate, two radicals R¹¹ may also be joined to form a 5- or 6-membered ring and/or may be substituted by halogen. In organosilicon substituents SiR¹² ₃, possible radicals R¹² are the same carboorganic radicals described above for R¹, where, if appropriate, two radicals R¹² may also be joined to form a 5- or 6-membered ring.

Preferred radicals R¹ are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl or phenyl, in particular methyl.

The substituents R³-R¹⁰ of the imine compound of the formula I or Ia, of the carbonyl compound of the formula II and of the aniline of the formula III can also be varied within a wide range. Possible carboorganic substituents R³-R¹⁰ are, for example, the following: C₁-C₂₂-alkyl which may be linear or branched, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5- to 7-membered cycloalkyl which may in turn bear a C₁-C₁₀-alkyl group and/or C₆-C₁₀-aryl group as substituent, e.g. cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C₂-C₂₂-alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C₆-C₂₂-aryl which may be substituted by further alkyl groups, e.g. phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5- or 2,6-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl, or arylalkyl which may be substituted by further alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, where, if appropriate, two radicals R³-R⁵ or two radicals R⁶-R¹⁰ may also be joined to one another to form a five-, six- or seven-membered ring and/or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S and/or the organic radicals R³-R¹⁰ may also be substituted by halogens such as fluorine, chlorine or bromine, amino NR¹¹ ₂, for example dimethylamino, N-pyrrolidinyl or picolinyl, alkoxy or aryloxy OR¹¹, e.g. methoxy, ethoxy or isopropoxy, or SiR¹² ₃. Furthermore, R³-R¹⁰ may be amino NR¹¹ ₂, for example dimethylamino, N-pyrrolidinyl or picolinyl, alkoxy or aryloxy OR¹¹, e.g. methoxy, ethoxy or isopropoxy, or halogens, such as fluorine, chlorine or bromine. Possible substituents R¹¹ are the same carboorganic radicals described above for R¹-R², where, if appropriate, two radicals R¹¹ may also be joined to form a 5- or 6-membered ring and/or be substituted by halogen. In organosilicon substituents SiR¹² ₃, possible radicals R¹² are the same carboorganic radicals described above for R¹-R², where, if appropriate, two radicals R¹² may also be joined to form a 5- or 6-membered ring, e.g. trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, tri-tert-butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl.

Preferred radicals R³-R⁵ are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl, phenyl, fluorine, chlorine and bromine, in particular hydrogen.

Preferred radicals R⁶-R⁷ are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl, phenyl, fluorine, chlorine and bromine. R⁶ is particularly preferably fluorine, chlorine and bromine and R⁷ is particularly preferably a C₁-C₂₀-alkyl group, with R⁷ preferably being bound to the aryl ring via a primary or secondary, preferably primary, carbon atom.

Preferred radicals R⁸ and R¹⁰ are hydrogen, methyl, ethyl, n-propyl, fluorine, chlorine and bromine, in particular hydrogen. R⁸ and R¹⁰ are preferably identical.

Preferred radicals R⁹ are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl, phenyl, fluorine, chlorine and bromine, in particular hydrogen, methyl, fluorine, chlorine or bromine, very particularly preferably chlorine.

For the purposes of the present patent application, a primary carbon atom is a carbon atom having the following substitution pattern —CH₂-R, where R is a linear, branched or cyclic hydrocarbon radical having 1-30 carbon atoms, preferably C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or hydrogen, particularly preferably C₁-C₁₉-alkyl or hydrogen.

For the purposes of the present patent application, a secondary carbon atom is a carbon atom having the following substitution pattern —CH—R₂, where R is a linear, branched or cyclic hydrocarbon radical having 1-30 carbon atoms, preferably C₁-C₁₉-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or hydrogen, particularly preferably C₁-C₁₉-alkyl or hydrogen.

Preferred anilines of the formula III are 2-chloroaniline, 2-bromoaniline, 2,6-dichloroaniline, 2,4-dichloro-6-methylaniline or 2,6-dibromoaniline. Preference is given to R⁶ or R⁷ being a halogen, in particular chlorine or bromine.

The molar ratio of the carbonyl compound II to the amine G-NH₂ used or the aniline of the formula III is generally from 1:5 to 1:0.8, preferably from 1:2 to 1:0.9 and particularly preferably from 1:1 to 1:1.2. The order of addition of the individual components is not critical. Thus, for example, the carbonyl compound can be initially charged and the amine G-NH₂ or the aniline of the formula III can be added thereto.

To accelerate the reaction, it is possible to add a catalytic amount of an acid catalyst, for example C₁-C₁₀-carboxylic acids such as formic acid or acetic acid, sulfonic acids such as para-toluenesulfonic acid, also HCl, HBr, HI or H₂SO₄. The molar ratio of carbonyl compound II to acid catalyst is preferably in the range from 1:0.00001 to 1:0.01, preferably from 1:0.0001 to 1:0.001. Furthermore, it is possible to add reagents for absorbing the water formed in the reaction, for example molecular sieves, phosphorus pentoxide or Si(OR)₄, where R is a C₁-C₁₀-alkyl group.

The phosphorus pentoxide can be used as the pure substance or as a mixture with an inert solid such as aluminum oxide, silica gel or aluminosilicate. Such mixtures are commercially available under the trade name Sicapent. The molar ratio of carbonyl compound II to phosphorus pentoxide is preferably in the range from 1:0.1 to 1:100, preferably from 1:1 to 1:10 and particularly preferably from 1:1.5 to 1:3. The ratio of Sicapent (about 50% by weight water uptake capacity) to carbonyl compound II is preferably in the range from 1 g of Sicapent per 0.1 mmol of carbonyl compound II to 1 g of Sicapent per 100 mmol of carbonyl compound II, preferably from 1 g of Sicapent per 1 mmol of carbonyl compound II to 1 g of Sicapent per 10 mmol of carbonyl compound II and particularly preferably from 1 g of Sicapent per 1.8 mmol of carbonyl compound II to 1 g of Sicapent per 6 mmol of carbonyl compound II.

The order of addition of the phosphorus pentoxide is not critical; it is preferably added to the mixture of carbonyl compound II and primary amine G-NH₂. The total amount of phosphorus pentoxide to be used can be added at the beginning of the reaction, or it can be added at intervals in a plurality of portions during the ongoing reaction. It has been found that the process proceeds particularly quickly when the total amount of phosphorus pentoxide is added at the beginning of the reaction.

The order of addition of the acid catalyst and/or the reagent for the absorption of water is not critical; it is preferably added to the mixture of carbonyl compound II and amine G-NH₂.

As solvents, use is usually made of aliphatic hydrocarbons such as pentane such as n-pentane, hexane such as n-hexane and isohexane, heptane such as n-heptane, octane such as n-octane, benzene, toluene, ethylbenzene, halogenated hydrocarbons such as dichloromethane or oxygen-comprising hydrocarbons such as diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol ethers, methanol, ethanol or isopropanol or mixtures thereof. Preference is given to using methanol, toluene or heptane when catalytic amounts of an acid catalyst are added. Preference is given to using ethers and in particular tetrahydrofuran when phosphorus pentoxide is added.

It has been found to be advantageous, particularly in the preparation of imine compounds of the formula Ia having halogen-comprising substituents on the aniline, to carry out the synthesis under a protective gas atmosphere such as nitrogen or argon.

The reaction is generally carried out at from 18 to 150° C., preferably from 30 to 110° C. and particularly preferably from 50 to 90° C. The reaction time is usually in the range from 30 minutes to 15 days, preferably from 5 hours to 5 days, particularly preferably from 8 hours to 3 days.

The work-up is carried out in a customary manner, e.g. by the filtering of the product before or after removing the solvent under reduced pressure. Purification of the product obtained can subsequently be carried out in the usual ways, for example by means of chromatography or recrystallization. An advantage of the reaction in aliphatic, nonaromatic solvents is the purity of the product obtained directly after filtration, which makes a further work-up unnecessary.

Carbonyl compounds of the formula II are prepared, for example, from 2,6-dibromopyridine as described in J. Organomet. Chem. 1973, 56, pp. 53-66.

The imine compound of the formula I can be reacted with carbonyl compounds of the formula V to form imine compounds of the formula IV.

We have accordingly found a process for preparing imine compounds of the formula IV,

where the variables have the following meanings:

-   R¹-R² are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical or a five-, six- or seven-membered heterocycle     comprising at least one atom from the group consisting of N, P, O     and S, where the organic radicals R¹-R² may also be substituted by     halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or the two radicals R¹-R² may     also be joined to R³-R⁵ to form a five-, six- or seven-membered     ring, -   R³-R⁵ are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical, NR¹¹ ₂, OR¹¹, halogen, SiR¹² ₃ or a five-, six- or     seven-membered heterocycle comprising at least one atom from the     group consisting of N, P, O and S, where the organic radicals R³-R⁵     may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or     two radicals R³-R⁵ may also be joined to one another to form a     five-, six- or seven-membered ring and/or two radicals R³-R⁵ may be     joined to one another to form a five-, six- or seven-membered     heterocycle comprising at least one atom from the group consisting     of N, P, O and S, -   the radicals R¹¹ are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical or SiR¹² ₃, where the organic radicals R¹¹ may also be     substituted by halogens and two radicals R¹¹ may also be joined to     form a five- or six-membered ring and the radicals R¹² are each,     independently of one another, hydrogen, C₁-C₂₂-alkyl,     C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1 to 10 carbon     atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical     and two radicals R¹² may also be joined to form a five- or     six-membered ring. -   G is C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₄₀-aryl, arylalkyl having     from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms     in the aryl radical, NR¹¹ ₂, SiR¹² ₃ or a five-, six- or     seven-membered heterocycle comprising at least one atom from the     group consisting of N, P, O and S, where the organic radical G may     also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃, E¹-E³ are     each, independently of one another, carbon, nitrogen or phosphorus,     in particular carbon, and -   u is 0 when E¹-E³ is nitrogen or phosphorus and is 1 when E¹-E³ is     carbon,     which comprises the following steps: -   a) reaction of an imine compound of the formula I,

with a metal alkyl of the formula M^(1A) _(R) ^(1A) _(X) ^(1A) _(n), where

-   M^(1A) is Li, Na, K, Mg, Ca, Sr or Ba, in particular Li, -   X^(1A) is C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl     having from 1 to 10 carbon atoms in the alkyl radical and 6-20     carbon atoms in the aryl radical, fluorine, chlorine, bromine,     iodine, hydrogen, NR^(2A) ₂, OR^(2A), SR^(2A), SO₃R^(2A),     OC(O)R^(2A), CN, SCN, where the organic radical X^(1A) may also be     substituted by halogens, -   R^(1A)-R^(2A) are each C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or     arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and     6-20 carbon atoms in the aryl radical, where the organic radicals     R^(1A)-R^(2A) may also be substituted by halogens, and -   n is 0 when MIA is Li, Na or K and is 1 when MIA is Mg, Ca, Sr or Ba     and -   b) subsequent reaction of the product obtained from step a) with a     carbonyl compound of the formula V

R^(3A)—C(O)X^(2A),

where

-   -   X^(2A) is fluorine, chlorine, bromine, iodine, OM^(3A), NR^(4A)         ₂, OR^(4A), SR^(4A) or OC(O)R^(4A), where the organic radical         X^(2A) may also be substituted by halogens,

-   R^(3A) is hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl,     arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and     6-20 carbon atoms in the aryl radical or SiR^(4A) ₃, where the     organic radical R^(3A) may also be substituted by halogens, and     -   the radicals R^(4A) are each, independently of one another,         C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having         from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon         atoms in the aryl radical and two radicals R^(4A) may also be         joined to form a five- or six-membered ring and     -   M^(2A) is Li, Na or K.

Preference is given to using imine compounds of the formula Ia, giving imine compounds of the formula IVa

where the variables have the following meanings:

-   R¹-R² are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical or a five-, six- or seven-membered heterocycle     comprising at least one atom from the group consisting of N, P, O     and S, where the organic radicals R¹-R² may also be substituted by     halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or the two radicals R¹-R² may     also be joined to R³-R⁵ to form a five-, six- or seven-membered     ring, -   R³-R¹⁰ are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical, NR¹¹ ₂, OR¹¹, halogen, SiR¹² ₃ or a five-, six- or     seven-membered heterocycle comprising at least one atom from the     group consisting of N, P, O and S, where the organic radicals R³-R¹⁰     may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or     two radicals R³-R⁵ or two radicals R⁶-R¹⁰ may also be joined to one     another to form a five-, six- or seven-membered ring and/or two     radicals R³-R⁵ or two radicals R⁶-R¹⁰ may be joined to one another     to form a five-, six- or seven-membered heterocycle comprising at     least one atom from the group consisting of N, P, O and S, -   the radicals R¹¹ are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical or SiR¹² ₃, where the organic radicals R¹¹ may also be     substituted by halogens and two radicals R¹¹ may also be joined to     form a five- or six-membered ring and -   the radicals R¹² are each, independently of one another, hydrogen,     C₁-C₂₂-alkyl, C₂-C₂₂alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1     to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the     aryl radical and two radicals R¹² may also be joined to form a five-     or six-membered ring, -   E¹-E³ are each, independently of one another, carbon, nitrogen or     phosphorus, in particular carbon, and -   u is 0 when E¹-E³ is nitrogen or phosphorus and is 1 when E¹-E³ is     carbon.

The definition of the variables R¹-R¹², G and E¹-E³ and their preferred embodiments is the same as given further above for the imine compounds of the formulae I and Ia.

The metal alkyls M¹R^(1A)X^(1A) _(n) are commercially available from FlukaAldrich or can be obtained, for example, by reaction of the corresponding R^(1A) halide with the metal M^(1A). Particular preference is given to lithium alkyls having a C₁-C₂₂-alkyl group, in particular a C₁-C₈-alkyl group, e.g. n-butyllithium or tert-butyllithium.

The halogen atom A of the imine compound I or Ia is usually replaced by M¹X^(1A) _(n) by metal-halogen exchange with the metal alkyl M¹R^(1A)X^(1A) _(n). Particularly suitable metal alkyls are lithium alkyls, magnesium alkyls, magnesium (alkyl) halides or mixtures thereof. The molar ratio of metal alkyl to imine compound I or Ia is usually in the range from 0.4:1 to 100:1, preferably in the range from 0.9:1 to 10:1 and particularly preferably from 0.95:1 to 1.1:1. Examples of such reactions are described, inter alia, by Furukawa et al. in Tet. Lett. 28 (1987), 5845.

As solvents in reaction step a), it is possible to use all aprotic solvents, in particular aliphatic and aromatic hydrocarbons such as n-pentane, n-hexane, isohexane, n-heptane, isoheptane, decalin, benzene, toluene, ethylbenzene or xylene or ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dimethoxyethane or diethylene glycol dimethyl ether and mixtures thereof. The reaction can be carried out at temperatures of from −100 to +160° C., in particular from −80 to 100° C. At temperatures above 40° C., preference is given to using aromatic or aliphatic solvents which contain no ethers or have only small proportions of ethers as solvents.

The product obtained from step a) can be isolated and purified or be used directly without further work-up in step b). The product obtained from step a) is preferably used in step b) without further work-up and without isolation.

As carbonyl compounds of the formula V, preference is given to using carboxamides in which X^(2A) is NR^(4A) ₂. The carbonyl compounds V are, for example, commercially available from FlukaAldrich.

The molar ratio of carbonyl compound V to imine compound I or Ia is usually in the range from 0.4:1 to 100:1, preferably in the range from 0.9:1 to 10:1 and particularly preferably from 0.95:1 to 1.1:1. Examples of such reactions are described, inter alia, by Brandsma, Preparative Polar Organic Chemistry, pp. 30-31 and pp. 142-143, Springer Verlag 1987.

As solvents in reaction step b), it is possible to use all aprotic solvents, in particular aliphatic and aromatic hydrocarbons such as n-pentane, n-hexane, isohexane, n-heptane, isoheptane, decalin, benzene, toluene, ethylbenzene or xylene or ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dimethoxyethane or diethylene glycol dimethyl ether and mixtures thereof. The reaction can be carried out at temperatures of from −100 to +160° C., in particular from −80 to 100° C. At temperatures above 40° C., preference is given to using aromatic or aliphatic solvents which contain no ethers or have only small proportions of ethers as solvents.

The process of the invention is particularly useful for anilines of the formula III having at least one halogen atom in the ortho position. Such anilines give only low yields of imine compound IV in toluene or alcohol.

The imine compounds of the formula IV or IVa obtained in this way can be reacted with further amine G-NH₂ or with further aniline of the formula III to give bis(imino) compounds. This synthetic route is particularly useful for preparing unsymmetrical bis(imino) compounds.

For the present purposes, unsymmetrical bis(imino) compounds are compounds which comprise at least two imino groups whose aryl radicals are not identically substituted. This is based on the substituents or the substitution pattern of the substituents under the theoretical assumption that the aryl radicals can rotate freely.

The preparation of the unsymmetrical bis(imino) compounds from imine compounds of the formula IV or IVa and further amine G-NH₂ or aniline of the formula III can be carried out under the same conditions as have been described for the process of the invention for preparing the imine compounds of the formula I or Ia.

Particularly preferred unsymmetrical bisimine compounds of the formula IV are 2-[1-(2,6-dimethylphenylimino)ethyl]-6-[1-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine, 2-[1-(2,4,6-trimethylphenylimino)ethyl]-6-[1-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine, 2-[1-(2,6-dimethylphenylimino)ethyl]-6-[1-(2-chloro-6-methylphenylimino)ethyl]pyridine, 2-[1-(2,4,6-trimethylphenylimino)ethyl]-6-[1-(2-chloro-6-methylphenylimino)ethyl]pyridine, 2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(2-chloro-6-methylphenylimino)ethyl]pyridine, 2-[1-(2,6-dimethylphenylimino)ethyl]-6-[1-(2,4-dibromo-6-methylphenylimino)ethyl]pyridine, 2-[1-(2,4,6-trimethylphenylimino)ethyl]-6-[1-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine, 2-[1-(2,6-dimethylphenylimino)ethyl]-6-[1-(2-bromo-6-methylphenylimino)ethyl]pyridine, 2-[1-(2,4,6-trimethylphenylimino)ethyl]-6-[1-(2-bromo-6-methylphenylimino)ethyl]pyridine and 2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(2-bromo-6-methylphenylimino)ethyl]pyridine.

The unsymmetrical bis(imino) compounds can be reacted further to form the corresponding titanium, zirconium, vanadium, chromium, iron or cobalt complexes. These are suitable as catalysts for the polymerization of olefins.

The process of the invention enables, in particular, even anilines having electron-pulling substituents to be converted into the corresponding monoimine compounds in good yields.

The imine compounds IVa are thermodynamically very stable and can be reacted with further aniline to form the unsymmetrical bisimine compounds. If imine compounds which are not substituted by electron-pulling radicals in the ortho position are used as starting materials, a further reaction with further aniline usually leads to mixtures of various symmetrical and unsymmetrical bisimine compounds.

A further advantage is that the process is also very well suited to the preparation of commercial quantities. Furthermore, 2,6-dibromopyridine is a cheaper starting material than, for example, 2,6-diacetylpyridine.

The following experimental examples serve to illustrate the invention without restricting the scope of the invention.

EXAMPLES Example 1 Preparation of 1-(6-bromopyridin-2-yl)ethylidene](2-chloro-4,6-dimethylphenyl)amine

1.00 g (0.0050 mol) of 1-acetyl-6-bromopyridine, 1.32 g (0.0085 mol) of 2,4-dimethyl-6-chloroaniline and 1 g of Sicapent were heated under reflux in 25 ml of tetrahydrofuran for 7.5 hours. After cooling, the insoluble solid was filtered off and washed with tetrahydrofuran. The solvent was distilled off from the filtrate obtained in this way and the residue was purified by column chromatography (aluminum oxide, neutral) (heptane:ethyl acetate=4:1), r_(f)=0.1. This gave 0.80 g (0.0024 mol) of the product in a yield of 48%.

Example 2 Preparation of 1-{6-[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridin-2-yl}ethanone

2.00 g (0.0059 mol) of [1-(6-bromopyridin-2-yl)ethylidene](2-chloro-4,6-dimethylphenyl)amine were dissolved in 25 ml of diethyl ether and cooled to −70° C. 3.70 ml (0.0059 mol) of a 1.6 M solution of butyllithium in hexane were added dropwise over a period of 15 minutes. The temperature rose to −40° C. and the mixture was stirred for another 30 minutes. The mixture was cooled to −70° C. and 0.52 g (0.0059 mol) of N,N-dimethylacetamide was added dropwise and the mixture was stirred at room temperature for another three hours. The reaction mixture was stirred with 5 ml of a saturated ammonium chloride solution. The aqueous phase was extracted twice with diethyl ether. The combined organic phases were dried over Na₂SO₄, filtered and the solvent was distilled off under reduced pressure. This gave 0.83 g (0.0028 mol) of the product in a yield of 47%.

Comparative Example 1 Preparation of 1-{6-[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridin-2-yl}ethanone in methanol

10 g of 2,6-diacetylpyridine (0.0613 mol), 9.54 g of 2-chloro-4,6-dimethylaniline (0.0613 mol) and 0.6 g of p-toluenesulfonic acid were heated under reflux in 400 ml of methanol for 90 minutes using a water separator. The solvent was distilled off completely and the residue was recrystallized twice from 50 ml of isopropanol. This gave 0.92 g (0.0031 mol) of 1-{6-[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridin-2-yl}ethanone in a yield of 5%.

The GC/MS indicated a product purity of 72%. 

1. A process for preparing imine compounds of the formula I,

where the variables have the following meanings: A¹ is chlorine, bromine or iodine, the radicals R¹ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radical R¹ may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or the radical R¹ may also be joined to R³ to form a five-, six- or seven-membered ring, R³-R⁵ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR¹¹ ₂, OR¹¹, halogen, SiR¹² ₃ or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radicals R³-R⁵ may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or two radicals R³-R⁵ may also be joined to one another to form a five-, six- or seven-membered ring and/or two radicals R³-R⁵ may be joined to one another to form a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, the radicals R¹¹ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or SiR¹² ₃, where the organic radicals R¹¹ may also be substituted by halogens and two radicals R¹¹ may also be joined to form a five- or six-membered ring and the radicals R¹² are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical and two radicals R¹² may also be joined to form a five- or six-membered ring, G is C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₄₀-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR¹¹ ₂, SiR¹² ₃ or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radical G may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃, E¹-E³ are each, independently of one another, carbon, nitrogen or phosphorus, and u is 0 when E¹-E³ is nitrogen or phosphorus and is 1 when E¹-E³ is carbon, which comprises the following steps: A) reaction of a carbonyl compound of the formula II

where the variables have the following meanings: A¹ is chlorine, bromine or iodine, the radicals R¹ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radical R¹ may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or the radical R¹ may also be joined to R³ to form a five-, six- or seven-membered ring, R³-R⁵ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR¹¹ ₂, OR¹¹, halogen, SiR¹² ₃ or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radicals R³-R⁵ may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or two radicals R³-R⁵ may also be joined to one another to form a five-, six- or seven-membered ring and/or two radicals R³-R⁵ may be joined to one another to form a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, the radicals R¹¹ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or SiR¹² ₃, where the organic radicals R¹¹ may also be substituted by halogens and two radicals R¹¹ may also be joined to form a five- or six-membered ring and the radicals R¹² are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical and two radicals R¹² may also be joined to form a five- or six-membered ring, E¹-E³ are each, independently of one another, carbon, nitrogen or phosphorus, and u is 0 when E¹-E³ is nitrogen or phosphorus and is 1 when E¹-E³ is carbon, with a primary amine G-NH₂, where the variables have the following meanings: G is C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₄₀-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR¹¹ ₂, SiR¹² ₃ or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radical G may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃, the radicals R¹¹ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or SiR¹² ₃, where the organic radicals R¹¹ may also be substituted by halogens and two radicals R¹¹ may also be joined to form a five- or six-membered ring and the radicals R¹² are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical and two radicals R¹² may also be joined to form a five- or six-membered ring.
 2. The process according to claim 1, wherein G is

where the variables have the following meanings: R⁶-R¹⁰ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR¹¹ ₂, OR¹¹, halogen, SiR¹² ₃ or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radicals R⁶-R¹⁰ may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or two radicals R⁶-R¹⁰ may also be joined to one another to form a five-, six- or seven-membered ring and/or two radicals R⁶-R¹⁰ are joined to one another to form a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, the radicals R¹¹ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or SiR¹² ₃, where the organic radicals R¹¹ may also be substituted by halogens and two radicals R¹¹ may also be joined to form a five- or six-membered ring and the radicals R¹² are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical and two radicals R¹² may also be joined to form a five- or six-membered ring.
 3. An imine compound of the formula I,

where the variables have the following meanings: A¹ is chlorine, bromine or iodine, the radicals R¹ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radical R¹ may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or the radical R¹ may also be joined to R³ to form a five-, six- or seven-membered ring, R³-R⁵ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR¹¹ ₂, OR¹¹, halogen, SiR¹² ₃ or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radicals R³-R⁵ may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or two radicals R³-R⁵ may also be joined to one another to form a five-, six- or seven-membered ring and/or two radicals R³-R⁵ may be joined to one another to form a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, the radicals R¹¹ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or SiR¹² ₃, where the organic radicals R¹¹ may also be substituted by halogens and two radicals R¹¹ may also be joined to form a five- or six-membered ring and the radicals R¹² are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical and two radicals R¹² may also be joined to form a five- or six-membered ring, G is C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₄₀-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR¹¹ ₂, SiR¹² ₃ or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radical G may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃, E¹-E³ are each, independently of one another, carbon, nitrogen or phosphorus, and u is 0 when E¹-E³ is nitrogen or phosphorus and is 1 when E¹-E³ is carbon.
 4. The imine compound according to claim 3 of the formula Ia,

where the variables have the following meanings: A¹ is chlorine, bromine or iodine, the radicals R¹ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radical R¹ may also be substituted by halogens, NR₁₁ ₂, OR¹¹ or SiR¹² ₃ and/or the radical R¹ may also be joined to R³ to form a five-, six- or seven-membered ring, R³-R¹⁰ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR¹¹ ₂, OR¹¹, halogen, SiR¹² ₃ or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radicals R³-R¹⁰ may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or two radicals R³-R⁵ or two radicals R⁶-R¹⁰ may also be joined to one another to form a five-, six- or seven-membered ring and/or two radicals R³-R⁵ or two radicals R⁶-R¹⁰ may be joined to one another to form a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, the radicals R¹¹ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or SiR¹² ₃, where the organic radicals R¹¹ may also be substituted by halogens and two radicals R¹¹ may also be joined to form a five- or six-membered ring and the radicals R¹² are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical and two radicals R¹² may also be joined to form a five- or six-membered ring, E¹-E³ are each, independently of one another, carbon, nitrogen or phosphorus, and u is 0 when E¹-E³ is nitrogen or phosphorus and is 1 when E¹-E³ is carbon.
 5. A process for preparing imine compounds of the formula IV,

where the variables have the following meanings: R¹-R² are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radicals R¹-R may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or two radicals R¹-R² may also be joined to R³-R⁵ to form a five-, six- or seven-membered ring, R³-R⁵ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR¹¹ ₂, OR¹¹, halogen, SiR¹² ₃ or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radicals R³-R⁵ may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or two radicals R³-R⁵ may also be joined to one another to form a five-, six- or seven-membered ring and/or two radicals R³-R⁵ may be joined to one another to form a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, the radicals R¹¹ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or SiR¹² ₃, where the organic radicals R¹¹ may also be substituted by halogens and two radicals R¹¹ may also be joined to form a five- or six-membered ring and the radicals R¹² are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical and two radicals R¹² may also be joined to form a five- or six-membered ring, G is C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₄₀-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR¹¹ ₂, SiR¹² ₃ or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radical G may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃, E¹-E³ are each, independently of one another, carbon, nitrogen or phosphorus, and u is 0 when E¹-E³ is nitrogen or phosphorus and is 1 when E¹-E³ is carbon, which comprises the following steps: a) reaction of an imine compound of the formula according to claim 3, with a metal alkyl of the formula M^(1A)R^(1A)X^(1A) _(n), where M^(1A) is Li, Na, K, Mg, Ca, Sr or Ba, X^(1A) is C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, fluorine, chlorine, bromine, iodine, hydrogen, NR^(2A) ₂, OR^(2A), SR^(2A), SO₃R^(2A), OC(O)R^(2A), CN, SCN, where the organic radical X^(1A) may also be substituted by halogens, R^(1A)-R^(2A) are each C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, where the organic radicals R^(1A)-R^(2A) may also be substituted by halogens, and n is 0 when M^(1A) is Li, Na or K and is 1 when M^(1A) is Mg, Ca, Sr or Ba, and b) subsequent reaction of the product obtained from step a) with a carbonyl compound of the formula V R^(3A)—C(O)X^(2A), where X^(2A) is fluorine, chlorine, bromine, iodine, OM^(3A), NR^(4A) ₂, OR^(4A), SR^(4A) or OC(O)R^(4A), where the organic radical X^(2A) may also be substituted by halogens, R^(3A) is hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or SiR^(4A) ₃, where the organic radical R^(3A) may also be substituted by halogens, the radicals R^(4A) are each, independently of one another, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical and two radicals R^(4A) may also be joined to form a five- or six-membered ring and M^(2A) is Li, Na or K.
 6. The process according to claim 5, wherein M^(1A) is Li.
 7. The process according to claim 5, wherein G is

where the variables have the following meanings: R⁶-R¹⁰ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR¹¹ ₂, OR¹¹, halogen, SiR¹² ₃ or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radicals R⁶-R¹⁰ may also be substituted by halogens, NR¹¹ ₂, OR¹¹ or SiR¹² ₃ and/or two radicals R⁶-R¹⁰ may also be joined to one another to form a five-, six- or seven-membered ring and/or two radicals R⁶-R¹⁰ are joined to one another to form a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, the radicals R¹¹ are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or SiR¹² ₃, where the organic radicals R¹¹ may also be substituted by halogens and two radicals R¹¹ may also be joined to form a five- or six-membered ring and the radicals R¹² are each, independently of one another, hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical and two radicals R¹² may also be joined to form a five- or six-membered ring. 